Apparatus for producing aldehyde free alcoholic liquids



APPARATUS FOR PRODUCING ALDEHYDE FREE ALCOHOLIC LIQUIDS Original Filed June 28, 1.926

Patented July 19, 1932 UNITED STATES PATENT OFF-ICE HERMAN EEUSER, OF CHICAGO, ILLINOIS original application filed June 28, 1926, Serial No. 119,057. Divided and this application filed November 8, 1928. Serial No. 318,096.

The present invention relates to the production of liquids contain ng ethyl alcohol derived by fermentation and WlllCh are free from aldehydes as well as from fusel oil and other toxic products of fermentation. Thus, my invention may be employed for the production of fermented malt liquids of the tonic or medicinal type as Well as of fermented fruit juice liquids when the manufacture thereof is permissible for sacramental, medicinal or other purposes or as an intermediate for the manufacture of other material.

The invention will be fully understood from the followin'gdescription, illustrated by the accompanying drawing, in which apparatus suitable for carrying the invention into effect is diagrammatically illustrated, partly in section.

In the manufacture of liquids of the type described above, and containing alcohol, it has not hitherto been recognized that the toxicity ordinarily ascribed to the alcohol is due to fusel oils and especially to aldehydes and like oxidized products, and that the same also have a distinct deleterious effect on other characteristics of the liquid. I have found that these accompanying materials are very toxic, particularly the aldehydes, the toxicity of which is apparently enhanced by their volatility and peculiar chemical reactivity. The absence of the toxic substance entirely deprives the material of physiological toxicity action, even with pure ethyl alcohol present in proportions as high as 3 t0 6%. Furthermore, I have found that certain of the deleterious physiological effects, as-well as other characteristics hitherto regarded as due solely'to the alcohol present in liquids,

particularly When in small proportions, are in fact due to the presence of aldehydes which I have found, by careful research and by the development of sensitive, accurate analytical tests, to be present in all alcoholic liquids including chemically pure alcohol as hitherto produced. The aldehydes may be formed during the manufacture of the li uid pr by subsequent oxidation (as by sur ace contact with air), and in aqueous solutions of alcohol as well as in other alcoholic liquids produced by fermentation or by subsequent distillation.

'By methods which I have discovered. and which are fully set forth hereinafter I have been able to produce and to retain in marketable form liquids containing alcohol and free, not only of fusel oil, but also of aldehydes, and hence free from toxic and intoxieating effect hitherto regarded a necessarily present in such material. My process and products are of particular value when the liquids are employed medicinally, owing to the absence of the toxic action of the aldehydes, etc., normally present.

In the following description of my inventi on, I have set forth a particular embodiment of apparatus and have, for convenience in de scription, referred to fermented malt-cereal liquid of suitable extract percentage, as the initial material. The initital material em- 7 ployed may be considered as containing 5% of alcohol by volume and the requisite extract percentage in the specific example set forth.

Referring to the drawing, the numeral 5 designates a kettle, shown partially in section, provided in its base with a steam-jacket 6. The upper portion of the kettle is suitably domed, as at 7, and is provided with a vapor-outlet pipe 8, which maysuitably lead to a condenser or open directly into the at- 30 mosphere, as desired. The vapor-outlet pipe 8 is suitably of goose-neck type, and the upper portion of the kettle 5, the dome 7, and the portion of the vapor-outlet pipe 8 from which condensate, if formed, may run back into the kettle are provided with lagging or thermal insulation of any suitable effective type, as indicated at 9, for the purpose of preventing condensation as hereinafter more fully set forth. The kettle is suitably provided 9a The upper with a manhole 10, a liquid gauge 11 and a thermometer 12, together with any other desired control and inspection devices. In the lower portion of the kettle there is provided a stirrer 13 mounted on a vertical shaft 14 which passes through a suitable stufiing box 15 in the bottom of the kettle, the shaft 14 being driven in any suitable manner, for example, by motor 16Vthrough speed reducer 17 and the gearing 18. The pipe 19 provided with valve 20 serves as an inlet to the interior of the kettle 5. The contents thereof may be discharged through the pipe 21 provided with valve 22. I

The liquid discharged through the pipe 21 may be directed in either of two paths, elther through line 23 provided with valve 24 to a continuous cooling device 25, or through the line 26 provided withvalve 27 to the kettle 28. It will be understood, of course, that when the liquid is discharged through the pipe 23, the valve 27 leading to the pipe 26 is closed; and that when the liquid is discharged through the pipe26 to the kettle 28, the valve 24, in the line 23 is closed.

In the flow of the liquid to the kettle 28, it passes through the pipe 26 into the pipe 29 leading into the bottom of the kettle, the latter pipe being provided with valve 30. branch pipe 31 provided'with valve 32 also connects with the'pipe 29, so that the contents of the kettle 28 may be discharged through The kettle 28 is in form generally similar to the kettle 5 already described, being provided in its base with a jacket 33 to which steam may be supplied through a valved pipe 34. The kettle 28 is likewise provided around its side walls with a jacket 35, which does not communicate with .the jacket 33, and to which water or other suitable cooling me dium may be suppled through the valved pipe 36, making its exit through the pipe 37. portion of the kettle 28 is domed, as at 39, and is provided with a vapor pipe 40, a valve 41 of gate or other suitable type being provided in the outlet pipe as close to the top of the kettle as is practicable so that, on closing the valve, the container or kettle is sealed substantially at the entrance of the vapor pipe. To prevent condensation, the upper portion of the kettle and the vaporoutlet pipe are lagged with any suitable thermal insulation, as indicated at 42. The kettle 28 is provided with any desired control and observation devices, for example, thermometer 43, liquid gauge Pi-and pressure gauge 45.

In the lower portion of the kettle 28 there is provideda stirrer 46, similar to the stirrer 13 provided in the kettle 5. The stirrer 36 is suitably mounted upon a rotatable vertical shaft 47 which passes through a stuffing box 48 in the bottom of the kettle, and is driven by any suitable device, for example, by the motor A tially equal capacity, until the pipes 29 and 31 from the system.

49 through the speed reducer 50 and the gearing 51. Within the kettle 28 there are likewise provided a-series of coils 52, to which brine or other suitable cooling medium may be supplied through the'inlet pipe 53 provided with valve 54. The cooling medium may make its exit from the coils 52 through the outlet pipe 55. A pipe 56, leading from any suitable source of carbon-dioxide under pressure, divides into two branches 57 and 58, the former leading to the upper portion of the kettle 28 and the latter into the kettle at its bottom. The line 57 is provided with a control valve 59 and a check valve 60. The line 58 is provided with a control valve 61 and a check valve 62. A vent '63 controlled by a valve is provided in the upper portion of the kettle. Samples of the contents of the kettle may be removed through the sampling cock 64.

In order that the invention may be clearly understood, it will be described in connection with the treatment of aspecific material, which may be, for example, a fermented liquid of a malt-cereal type containing initially about 5% of alcohol by volume. In starting operations, the fermented liquid is run into kettels 5 and 28, whichare of substanthey are each a little more than half full. Thus, if the capacity of each of the kettles is 200 barrels, 105 barrels may be run into each. The stirrers 13 and 46 in the two kettles are then started in operation and the liquid in each kettle is heated to boiling by supplying steam to the ackets in the bottoms of the kettles. The gate valve 41 of kettle 28 is kept open. Assuming that the liquid employed has an alcohol content of 5% by volume, it will be in boiling at 958 C. The kettles being on y alittle more than half full, ample room is provided for the foam formed at the beginning of boiling. Boiling is continued until the vapors given ofi from the liquid are free from the characteristic fusel oil odor, which is present in them in the beginning of the operation. In the specific instance cited, the liquid is entirely free from fusel oil and from aldehydes when it has been reduced to an alcohol content of 3.50% by volume, at which point its boiling oint at the altitude of Chicago is 97 C. T e volume of the liquid at this point is reduced, to about 100 barrels in each kettle at the boiling temperature. Corresponding to about 95.7 barrels of cold liquid in each kettle, 8.86% of liquid having been evaporated.

When the point is reached at which the fusel oil and aldehyde isremoved as above indicated,only sufficient steam is supplied to keep the liquid in the two'kettles sufiiciently hot (near the boiling point) to maintain a suflieient evolution of vapors to prevent access of air and aldehydes. During this entire operation, the lagging on the upper pornee-mace tion of the kettles prevent any return of reflux and aids inthe elimination ofaldehydes from the residue.

valve 41 is then closed While the residues in the two kettles are kept hot (near the boiling or simmering point), the valve 22 in the line 21, the valve 27 in the line 26 and the valve 30 in the line 39 are opened, and the entire body of residue from the kettle 5 .is discharged into the kettle 28. The fiow of residue continues until the level of liquid in the kettle 28 reaches the gate valve 41, which point can be readily observed by means of the gauge 44. The tightly, so that the kettle 28 is entirely sealed while filled with residue which is entirely freed of fusel oil and aldehydes and which contains no air or oxygen. At this stage the alcohol content of the residue is about 3.25 to 3.5% by volume. n

The residue'in the kettle 28 is then cooled preferably, first by passing cold Water through inlet pipe 36 to and through the jacket around the kettle and out through the outlet pipe 37. When the residue has been partially cooled, for example, to about 32 C. the flow of water through the cooling jacket 35 is stopped, it is preferably drained, and the cooling is continued by flowing cold brine through inlet pipe 53, coils 52 within the tank and out of the outlet pipe 55. It is thereby brought to a temperature of 2 C.

- or lower when cooling is stopped. The voldissolved and there previously passed through the top of the kettle,

ume of residue is reduced by cooling from 200 barrels hot residue to somewhat more than 191 barrels cold residue, the contraction being noted on the liquid gauge 44. In -the operation as described, the space in the kettle above the cooled residue is highly evacuated, it being understood that if the kettle has not sufiicient strength to withstand the strains set up by cooling, a gas completely free from oxygen, such as carbon-dioxide or nitrogen absorbing medium, may be permitted to enter for example, through the line 57, duringthe cooling operation. No oxygen is permitted to come in contact cooled in the presence of an oxygen containing gas, up to 0.40%

by volume of oxygen is is a substantial oxidation of the alcohol content to aldehydes, readily noticeable by the strong characteristic odor of a sample taken from the sampling cock 64.

After the residue has cooled, any vacuum or partial vacuum remaining in the kettle is broken by the introduction of carbon-dioxide through the lines 56 and 57 the carbon-dioxide being supplied, for example, under.

a pressure of about 25 lbs. gauge until a desired pressure is secured in the kettle. About 10 lbs. gauge has been found to be adequate.

be slightly opened at this an active oxygen liquid therethrough or by -to the cold storage room, where it may be stored in containers, from which air is preferably previously removed, for example, by means of carbon-dioxide. It may then be made ready for the market by carbonating, filtering, bottling and pasteurizing in the bottles. Other trade packages may be employed, but bottles are preferred because the access of oxygen to the liquid, with the resultant formation of aldehydes from its alcohol content is more easily prevented. If desired, a small proportion of-a phosphite or hypophosphite-or of hypophosphorus acid may be added to the materialbefore it is pack aged; for example, the equivalent of 4 to 12 grams of an alkali metal phosphite or hypo- Ehosghite may be so added per barrel of the If desired, instead of carbonating in the usual manner, the cooled liquid ma be carbonated in the kettle 28 in bulk. lifter the liquid has been cooled to the desired low temthe carbon-dioxide is allowed to enter the chamber from the line 56 through line 58, valve 61 and valve 62. The pressure within the kettle gradually rises until a pressure slightly under that of the source of carbondioxide is reached. In order to continue the flow of the carbon-dioxide, the vent 63 may point, a small amount of carbon-dioxide permitted to dioxide into the beverage produced. After the liquid has been carbonated, it may be packaged in any suitable manner in use in the trade, the same precautions being taken to escape anda continuous flow of the carbonavoid a'ccess of oxygen containing gas or air as has been previously mentioned.

- The heating or boiling of fermented liquids in the ordinary manner imparts thereto a burnt or empyreumatic taste and odor; but by operating in accordance with my invention in which air is not permitted access nor contact with the liquid or residue,"this burntgtaste and odor is avoided.

If desired, instead of carryingout the'operation in the manner aboveset forth, the liquid from the kettle 5, when completely deprived of the fusel oil and aldehydes present therein, may be discharged through the lines 21 and 23 through the cooler 25, the line having previously been freed from air or oxygen containing gas eitherv by passing an air-free flowing an air-free gas, such as carbon-dioxide therethrough.

During the time that any liquid remains in the kettle 5,

it must be kept at or sufficiently near the boiling point, so that air will not be permitted access to the liquid and absence of aldehyde formation in the liquid and return thereto assured.

. portion, the material may alcohol (by volume) has been removed. If

desired, the alcohol content of the residue may be supplemented by the addition thereto of an aldehyde-free ethyl, alcohol solution in water. Ordinary commercial ethyl alcohol or solutions containing it cannot be employed, as even when prepared under the most careful conditions as hitherto known, they contain detectable quantities of aldehydes capable of substantially affecting the toxicity and intoxicating action of the liquid. prefer, therefore, to prepare a solution of ethyl alcohol free from aldehyde, procedure above set forth in connection with the manufacture of thealdehyde and fusel oil free residue. kettles 5 and 28 with fermented liquids as hereinbefore set forth, they may be charged with an aqueous solution of chemically pure alcohol ,containing, say 5 to 50% alcohol and the operation conducted in exactly the manner above set, forth. An aldehyde-free alcoho solution containing 4% alcohol, or higher, depending upon the strength of the alcohol solution originally taken, may thus be produced and is found to differ markedly from a solution of alcohol made in the ordinary man ner being entirely free from any ordor or the usual alcohol sweetness. It is apparent that a sample of this liquid must be testedor examined at once upon withdrawal, as there is a rapid absorption of oxy en with a formation of quantities of ald ehytle which a preciably affects the taste and odor of t 0 liquid and are qualitatively and quantitatively detectable by sensitive methods of analysis. If it is desired that the liquid shall retain its characterist'cs or absence 0 aldehyde taste and flavor arid the absence resulting therefrom, it must be retained in containers from which air or other oxygen containing gases are excluded unless the ethyl alcohol content of. the beverage or liquid is less than 4% by volume. Below this probe in contact with air for an appreciable length of time without producing aldehydes.

In carrying out my invention, I prefer to apply indirect heat to the liquid under treat ment, as the use of direct steam injection for heating introduces substantial quantities of air or oxygen.

The operation may be conducted under greater or less vacuum, if desired; but I have found that, with reduction in pressure, it is necessary to cause a greater proportional evaporation of the alcohol (and hence of the liquid) than under atmospheric pressure to effect the removal of the fusel oil. Furthering heat to said container,

using the In place of charging the.

l the latter, thermal f coil, and stirring means free liquid from more, in operating in vacuo and in the subsequent handling of the liquid I have found that there is much greater difiiculty in securing freedom from aldehydes.

This application in a division of my application Serial No. 119,057, filed June 28, 1926.

I claim:

. 1. In apparatus for producing aldehydefree residues from alcoholic liquids, a contain-' er for a body of the liquid, means for supplystirring means within the container, a vapor outlet leading from the container, means for sealing the container off from its vapor outlet at substantially the entrance to the latter, thermal insulation surrounding theupper'portion of the I container and the adjacent portion of the vapor outlet, thereby preventing reflux to the container, and separate means for cooling the contents of the container.

2. In apparatus for free residue from alco tainer for a bulk supply of liquid, means for supplying heat thereto to heat the contents of the container, a va or outlet leading from the container, means or sealing the container from its outlet at substantially the entrance to insulation surrounding the upper portion of the container and the adjacent portions of the vapor outlet,.a closed coil within the container, and means for passing a cooling medium through said coil.

3. In apparatus for roducing aldehyde free residues from alco olic liquids, a container for a bulk supply of liquid, means for supplying heat thereto to evaporate the contents of the container, means for sealing the container from its outlet at substantially the entrance of the latter, thermal insulation surrounding the upper portion of the container and the adjacent ortions of the vapor outlet, a closed coil withm the container, and means for passing a cooling medium through said within said conolic liquids, a container. I 4. In apparatus for producing an aldehyde free liquid from an alcoholic li uid, a container for a bulk supply of liqui means for heating the container to boil said liquid, a vapor outlet from the container, means for sealing the container from its outlet at sub-- stantially theentrance to the latter, a second container, means for applying heat to the second container, a vapor outlet for the second container, and means for forcing the hot contents of the second container into the first container t'o fill the latter to its sealing means.

5. In apparatus for producing an aldehydean alcoholic liquid, a container for a bulk supply of liquid, means for heating the container to boil said liquid, a 'apor outlet from the container, means for sealing the container from its outlet at substantially the entrance to the latter, a second container, means for supplying heat to the roducing aldehydesecond container, a vapor outlet for the second container, means for forcing the hot contents of the second containermto the first container-to fill the latter to its sealing means, 5 and means within the first container for cooling the liquid contents thereof.

6. In apparatus for producing aldehydefree residues from alcoholic liquids, a container means for'supplying heat thereto to 10 evaporate its contents, a vapor outlet from the container, means for sealing oil the container from the outlet at substantially the entrance to the latter from the container, and separate means within the container for 15 cooling its contents.

HERMAN HEUSER. 

